Applied Physics A (2021) 127:312

https://doi.org/10.1007/s00339-021-04419-7

Insights into thermodynamic properties of CsCl‑type HfTM (TM = Fe,

Ru, Os) compounds from first‑principles calculations
Jin Zhang1 · Hao Guo1 · Anran Chen1 · Yao Zhou1 · Jie Yang1 · Chong Wang1 · Tao Sun1 · Yu Yang1

Received: 24 November 2020 / Accepted: 5 March 2021

© The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature 2021

Abstract
In this work, we used the first-principles calculations based on density functional theory and quasi-harmonic Debye to predict
the electronic structures, phonon dispersions and thermodynamic properties of HfTM (TM = Fe, Ru, Os) compounds. The
obtained phonon dispersions of HfTM indicate that they are thermodynamically stable. Moreover, HfFe, HfRu and HfOs show
metallic properties from the electronic structures. The bulk moduli and thermal expansion coefficients of HfTM compounds
under temperature of 0 ~ 1500 K and pressure of 0 ~ 20 GPa were considered, and the results indicate that the bulk modulus
reduces as the temperature increases, and thermal expansion coefficient changes quickly to temperature at low temperatures.
The order of thermal expansion coefficient is HfFe > HfRu > HfOs and that of thermal stability is HfOs > HfRu > HfFe.
Besides, Debye temperature is opposite to the trend of Grüneisen parameter under the same temperature and pressure.

Keywords First-principles calculations · Hafnium compounds · Electronic structure · Thermodynamic properties

1 Introduction Although the importance of CsCl-type compounds in

many technical applications is increasing, the computational
The CsCl-type compounds have many excellent proper- and experimental results of these alloys are few. With the
ties, such as high oxidation resistance and high-tempera- success of density functional theory [11], first-principles
ture strength, and therefore, they have attracted widespread calculations have been proven to be reliable and accurate
attentions [1–4]. Recently, great efforts have been made to methods for solving the ground-state properties of struc-
investigate the physical properties of CsCl-type compounds tural materials [12–19]. In recent years, the first-principles
composed by means of Group VIII (Ru and Os) and Group calculations based on density functional theory (DFT) were
IV (Ti, Zr and Hf) elements [5]. These CsCl-type com- used for material development and performance improve-
pounds have high melting points and relatively good high- ment [20–29]. For example, the ab initio calculations based
temperature properties. The experimental analyses show that on DFT were employed to investigate band structures, den-
the melting points of TiOs, ZrOs and HfOs are 2433, 2313 sity of states and formation enthalpies (ΔH) of HfTM com-
and 2861 K, respectively [5–7]; HfTM compounds have pounds [30]. A recent report about the structural, mechanical
high melting points, i.e., TiRu (2403 K), ZrRu (2403 K) properties of ZrTM, TiTM and HfTM (TM = Fe, Ru and Os)
and HfRu(2723 K) [8]. Owing to the high neutron section, compounds showed that these compounds are anisotropic in
CsCl-type hafnium compounds are widely applied in control elastic modulus [31]. The structural, electronic and mechani-
rods [9]. Besides, some Hf and other transition metals (Co, cal of HfTM (TM = Rh, Ru and Tc) have been discussed
Pd, Fe and Pt) compounds have been regarded as energy using the pseudo-potential via VASP codes based on DFT
materials, because they are capable of forming hydrides with [32]. However, these investigations are mainly focused on
high hydrogen to metal ratio [10]. the structural, electronic and thermodynamic properties of
HfTM compounds. Moreover, most of the above investiga-
tions were conducted at T = 0 K and P = 0 GP, and ther-
* Tao Sun
[email protected] mal effects were not considered in these calculations. As
the high-temperature compounds, it is essential to discuss
1
National Center for International Research On Photoelectric the performance of the CsCl-type HfTM compounds under
and Energy Materials, School of Materials and Energy,
Yunnan University, Kunming 650091, China

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more complex conditions, such as different temperatures and 2 × 2 × 2 supercell, and the k-points and energy cutoff energy
pressures. were 450 eV and 10 × 10 × 10, respectively. The thermody-
Therefore, for checking the validity and reliability of the namic properties of these HfTM compounds were calculated
computational method in the current work, we employed employ to quasi-harmonic Debye model within the Gibbs
the first-principles calculations to investigate the electronic code [37]. In this model, Gibbs free energy G*(V, P, T) in
structures, phonon dispersions of HfTM compounds in the the non-equilibrium state was determined by the following
ground state, which are in fact revisits of the previously definition:
reported results [30–32]. Most importantly, in this work,
the dependence of thermodynamic properties, i.e., Debye
G ∗ (V, P, T) = Avib (Θ(V), T) + PV + E(V) (1)
temperature (ΘD), thermal expansion coefficient and Grü- Here Avib, PV and E(V) represent the vibrational Helmholtz
neisen parameter, of HfTM compounds on temperature free energy, the constant pressure and the total energy of
and pressure was highlighted. Here, the calculation method cell, respectively. The expressions of bulk modulus (B), heat
was introduced in the second section, and the stability, bulk capacity of constant volume (Cv), Debye temperature (θD),
modulus and other thermodynamic properties of these com- and Grüneisen parameter (γ) and thermal expansion coef-
pounds were discussed in the third part. We aim to provide ficient (α) can be observed in the reported literature [38].
some reference for future works of these compounds.

2 Computational details 3 Results and discussion

Here, the first-principles calculations, which are in view of 3.1 Electronic structures

density functional theory frame [33], were employed to dis-
cuss the structural, electronic and thermodynamic proper- The crystal structure of HfTM compounds is shown in
ties of HfTM compounds using the CASTEP code [34]. The Fig. 1. It can be found that HfTM compounds crystallize as
interaction between the valance electrons and ionic core was the body-centered cubic structure, the TM atoms situate at
characterized by the ultrasoft pseudopotentials (USPP) [35]. the cube corner, and the Hf atom occupies the cubic cent-
The generalized gradient approximation (GGA) with Per- ers sites. The crystal structure of HfTM compounds was
dew–Burke–Ernzerhof (PBE) scheme was used to represent geometry optimized firstly before the calculations, and the
the exchange–correlation energy [36]. The valence–elec- optimized results are shown in Table 1, as well as the experi-
tron configurations were Hf 5p65d26s2, Fe 3p63d64s2, Ru mental results [39, 40] and other theoretical data [30–32, 41,
4p64d75s1 and Os 5p65d66s2. In the present calculation, 42]. The optimized results show that no change in symmetry
the cutoff energy was 500 eV. For HfTM compounds, the can be observed, and the variations of lattice parameters
k-points of Brillouin zone (BZ) were 16 × 16 × 16. Toler- are less than 2%, revealing that the setting computational
ances of total energy and force per atom were 5 × ­10–7 eV/ parameters are credible.
atom and 0.01 eV/atom, respectively. Using the linear The electronic structures of HfTM compounds, including
response method applied the norm-conserving pseudo- band structure, density of state (DOS) and electron density
potential, the phonon calculations were performed with a difference, were investigated for a better understanding the

Fig.1  Crystal structures of
HfTM (TM = Fe, Ru, Os)
compounds: a Side view, b
three-dimensional view

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Table 1  Theoretic lattice a V B0 B’ B’’ Bond Population Length Refs

parameters (a in Å and V in Å3),
population, bond length (in Å), HfFe 3.146 31.137 171.4 4.183 − 0.0248 Hf-Fe 1.59 2.725 Present
bulk modulus at 0 GPa B0 (in
3.144 – 177 – – – – – [30]
GPa), the pressure derivation
of bulk modulus B’ and the 3.147 31.155 167.7 – – – – – [31]
­ Pa−1)
implied value B’’ (in G HfRu 3.254 34.455 206.3 3.663 − 0.0187 Hf-Ru 1.66 2.818 Present
of HfTM (TM = Fe, Ru, Os) 3.245 – – – – – – – [30]
compounds
3.255 34.476 199.9 – – – – – [31]
3.239 – – – – – – – [32]
3.225 – – – – – – – [39]
HfOs 3.264 34.774 225.8 4.286 − 0.0193 Hf-Os 1.79 2.827 Present
3.265 34.794 231.2 – – – – – [31]
3.239 – – – – – – – [40]
3.294 – 223.7 – – – – – [41]
3.257 – 224.43 – – – – – [42]
– 234.3 4.43 – – – – [43]

physical properties of HfTM compounds. The calculated thereby indicating that there are strong hybridizations
band structures of HfTM compounds near the Fermi level between Hf-d and TM-d orbitals to form strong Hf-TM
are shown in Fig. 2. The dotted line at zero point represents chemical bonds. It should be noted that Fe, Ru and Os are
Fermi level. The part of band structure above Fermi level the same group of elements, and thus, the electronic struc-
is conduction band (CB), while that below Fermi level is tures of these HfTM compounds, such as band structure and
valence band (VB). It can be seen that there is no obvious DOS, are very similar. This similarity of electronic struc-
band gap between CB and VB. It can prove that these HfTM tures will lead to that the physical properties of these HfTM
compounds are metallic. compounds are similar.
Figure 3 plots the total and partial density of states To demonstrate the interaction and bonding properties
(TDOS and PDOS) of HfTM compounds. In Fig. 3, the between Hf and TM atoms, the electron density differences
dotted line represents Fermi level. Similarly, no gap can be of HfTM compounds were investigated and are plotted in
found in TDOS at Fermi level, which also prove that these Fig. 4. The electron density ranges from − 0.2 to 0.2 e/Å3,
HfTM compounds are metallic. Generally, the TDOS val- and the red region represents the accumulation of electrons,
ley at Fermi level is defined as pseudogap, and the presence while the blue region represents the lack of electrons [44].
of pseudogap corresponds to the phase stability of solids. From Fig. 4, one can see that there is electron accumula-
Therefore, these HfTM compounds are stable. Besides, as tion between Hf and TM atoms, indicating the formation
shown in Fig. 3, the TDOS near Fermi level of each HfTM of strong Hf-TM chemical bonds. Besides, the gathering
compounds is mainly made up of Hf-5d and TM-d states, electrons between Hf and TM atoms are along the [111]

Fig. 2  Band structures of HfTM compounds: a HfFe, b HfRu and c HfOs

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Fig. 3  Total densities of states (TDOS) and partial densities of states (PDOS) of HfTM compounds: a HfFe, b HfRu and c HfOs. The vertical
dot lines represent the Fermi level

Fig. 4  The electron density dif-

ferences of HfTM compounds

direction. The bond population values of Hf-Fe, Hf-Ru and implied B’’, along with the previous theoretical data [31,
Hf-Os bonds in Table 1 are 1.59, 1.66 and 1.79, respectively. 41–43]. Obviously, our fitting values of HfTM compounds
The high bond population indicates the covalent bond, and are in good consistent with the reported ones.
the higher bond population represents the stronger covalency Figure 6 plots the bulk moduli of HfTM compounds
of bond. Therefore, Hf-TM chemical bonds are covalent under different pressures and different temperatures. From
bonds, and the Hf-Os bond is the most covalency. Moreo- Fig. 6, it can be clearly found that B has a close relation-
ver, the bond lengths of Hf-Fe, Hf-Ru and Hf-Os bonds are ship with temperature and pressure, indicating that these
2.725, 2.818 and 2.827 Å, respectively, which indicate the HfTM (TM = Fe, Ru, Os) compounds are inharmonic crys-
bond strength is in the sequence of Hf-Fe < Hf-Ru < Hf-Os. tals. Moreover, at T < 100 K, bulk modulus B of each HfTM
changes slightly; while the temperature T > 100 K, the B
3.2 Fundamental parameters value significantly decreases. This may originate from that
the atomic distance increases with the temperature improves,
Here, the fundamental properties of HfTM compounds at the and the atomic spacing and the compressibility increase.
temperature from 0 ~ 1500 K and the P from 0 ~ 20 GPa were The compressibility and bulk modulus have the opposite
obtained by calculating the relationship between volume V trend, and thus bulk modulus B reduces as the steady tem-
and the energy E. Then, the third-order Murnaghan equation perature. Furthermore, it can be clearly found that the bulk
of state [45] was used to fit the E-V curve. The fitting curves modulus enhances significantly with pressure. This also can
are shown in Fig. 5. It can be found that the fitted curves be explained from the variation of atomic distance that the
agree well with the E-V data. increasing pressure causes the atomic distance to decrease,
Table 1 also lists the fitting results, including bulk modu- further leads to the decrease in compressibility and finally
lus B0, the derivation of bulk modulus to pressure B’, the results in the increase in bulk modulus.

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Fig.5  Total energy as a function of volume of HfTM compounds. a HfFe, b HfRu and c HfOs. Squares are the calculated values, and lines are
the fitted values by third-order EOS

Fig. 6  Variations of bulk moduli with the temperature at different pressures. a HfFe, b HfRu and c HfOs

3.3 Phonon dispersion temperature ΘD can be obtained [46]. The phonon disper-

sions of HfTM (TM = Fe, Ru, Os) compounds are shown in
The phonon dispersion curve can give a lot of important Fig. 7. Taking HfOs as an example, the phonon dispersions
information about the lattice dynamics of materials. Based and densities of states at equilibrium, compression (-10%)
on phonon properties, the constant pressure Cp, constant and expansion (+ 10%) states are plotted in Fig. 7c. It is
volume C v, thermal expansion coefficient α and Debye obvious that the phonon dispersion curves do not show

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 312 Page 6 of 11 J. Zhang et al.

Fig. 7  Phonon dispersion curves and phonon densities of states expanded state with 10% expansion in volume, and compressed state
(PHDOS) of HfTM compounds. a HfFe, b HfRu and c HfOs. In the with 10% compression in volume, respectively
graph c, the green, red and blue dotted lines are the equilibrium state,

soft modes, indicating that HfOs is thermodynamically other, thereby resulting in a small overlap of the optical
stable at such large deformations. As shown in Fig. 1, the and acoustic branches of HfOs, as shown in Fig. 7c.
unit cell of HfTM compounds contains two atoms, and Figure 8 shows the equilibrium-state enthalpy (H), Gibbs
therefore, there are six phonon dispersion curves. In these free energy (G) and entropy (S) of HfTM compounds. These
six phonon dispersion curves, two curves are acoustic HfTM compounds show the similar H, G and S due to their
modes and four curves are optical modes. It can be found similar phonon dispersion curves. The standard formation
in Fig. 7a, b that there are no soft modes on phonon dis- enthalpy of HfRu by high-temperature calorimetry at 1400 K
persion curves of HfFe and HfRu, indicating that HfFe is 183.5 ± 10.4 kJ·mol−1 [47]. In this work, the calculated
and HfRu are also thermodynamically stable. The rela- formation enthalpy of HfRu at 1400 K is 197.16 kJ·mol−1.
tive molecular masses of Hf and TM (TM = Fe and Ru) As can be clearly seen from Fig. 8, the enthalpy and
are quite different, revealing that the optical and acoustic entropy increase as the temperature increases. Meanwhile,
branches are separate: The optical branches are mainly the enthalpy (H) increases slightly faster than entropy (S)
contributed from TM (TM = Fe and Ru), and the acoustic at high temperatures. Moreover, according to G = H—TS,
branches originate from Hf (as shown Fig. 7a, b). The Gibbs free energy G decreases with the increasing tempera-
relative molecular masses of Hf and Os are close to each ture. Besides, at the same temperature, Gibbs free energies

Fig. 8  a enthalpy H, b Gibbs free energy G and c entropy S of HfTM (TM = Fe, Ru, Os) compounds

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G of these three HfTM compounds show a relationship of heat capacities (Cv and Cp) of HfTM compounds as function
HfOs < HfRu < HfOs, which also indirectly illustrate that the of temperatures and pressures are shown in Figs. 9 and 10.
sequence of phase stability is HfOs > HfRu > HfFe. For HfTM compounds, since there are two atoms in each
unit cell, their Dulong–Petit limits are 50 J·mol−1·K−1. From
3.4 Heat capacity Fig. 9, with the increase in temperature, the increasing speed
of Cv decreases, and when the temperature is close to ΘD, Cv
The constant pressure heat capacity (Cp) and constant vol- reaches the Dulong–Petit limit of 50 J·mol−1·K−1 [48]. This
ume heat capacity (Cv) play an important role in the ther- is a very common phenomenon for materials at such elevated
modynamic properties of materials. Therefore, these two temperature. Furthermore, at T < ΘD, the Cv value of each

Fig. 9  Heat capacities Cv as a function of pressure and temperature of HfTM compounds. a HfFe, b HfRu and c HfOs

­ p as a function of pressure and temperature of HfTM compounds. a HfFe, b HfRu and c HfOs
Fig. 10  Heat capacities C

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HfTM (TM = Fe, Ru, Os) compounds decreases slightly with the thermal expansion coefficient in the temperature range
the increasing pressure. Thus, when the temperature is lower of 0 ~ 1500 K and the pressure range of 0 ~ 20 GPa were
than Debye temperature, the pressure has a very slight effect discussed.
on Cv, while the temperature can greatly affect Cv. The relationships between volume V, temperature T and
The Cp value of solids can provide important information pressure P are shown in Fig. 11. The sequence of volume of
on the lattice vibration characteristics. Figure 10 shows the HfTM compounds at the same temperature and pressure is
variations of Cp of HfTM (TM = Fe, Ru, Os) compounds HfFe < HfRu < HfOs. It can be clearly observed from Fig. 11
under various pressures and temperatures. Compared to that the volume is positively correlated with temperature,
Fig. 9, it can be found that the changes in Cp and Cv are and at the same pressure, the volume increases with the tem-
similar when the temperature is in the low range. However, perature. The variation of volume is related to the change of
when the temperature rises to that larger than Debye temper- atomic distance under different temperature and pressure,
ature, the trends of Cp and Cv show a significant difference. which have been discussed above.
Cp is not close to a constant as Cv is, but continues to show Figure 12 plots the thermal expansion coefficients α under
a slowly upward trend. As is known, Cv stands for the con- different temperatures and pressures. From Fig. 12, the α
stant volume heat capacity, while Cp stands for the constant values of HfTM (TM = Fe, Ru, Os) compounds increase
pressure heat capacity. For Cv, the volume does not change almost linearly at low temperatures, satisfying the quasi-
when the temperature reaches to ΘD, but for Cp, the volume harmonic approximation at the high T limit [49]. Mean-
still enhances. Thus, Cp is greater than Cv at the temperature while, the thermal expansion coefficient at 0 GPa for each
higher than ΘD. The interaction among Cp and Cv also can be HfTM is the largest under the same temperature. Under 0
expressed by Cp-Cv = (3α)3BTV, in which α, B, T and V are GPa and 1500 K, the α value of HfFe, HfRu and HfOs is
thermal expansion coefficient, bulk modulus, temperature 4.05 × ­10–5 K, 2.50 × ­10–5 K, and 2.46 × ­10–5 K, respectively,
and volume, respectively. This relationship indicates that Cp and therefore, the order of thermal expansion coefficient is
is larger than Cv. Besides, it can be found from Fig. 10 that HfFe > HfRu > HfOs. Generally, thermal stability is related
Cp is different from Cv that Cp is greatly affected by pres- to α value that a larger α value corresponds to a worse ther-
sure, that is, Cp and pressure have opposite trends. mal stability. As a result, the thermal stability of these com-
pounds is HfOs > HfRu > HfFe.
3.5 Thermal expansion coefficient Debye temperature is a physical constant of matter that
characterizes numerous properties of solids, such as spe-
In order to investigate the influence of temperature T and cific heat, electric conductivity, thermal conductivity and
pressure P on thermal expansion coefficient and Debye elastic properties. It indicates the approximate tempera-
temperature of HfTM compounds in detail, the changes of ture limit below which quantum effects may be observed.

Fig. 11  Variations of volume as a function of temperature and pressure of HfTM compounds. a HfFe, b HfRu and c HfOs

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Fig. 12  Variations of thermal expansion coefficients as a function of temperature and pressure of HfTM compounds. a HfFe, b HfRu and c HfOs

Fig. 13  Variations of Debye temperature as a function of temperature and pressure of HfTM compounds. a HfFe, b HfRu and c HfOs

Figure 13 shows the change in Debye temperature under with the increase in temperature, and then the ΘD val-
different pressures and temperatures. The calculated ues decrease almost linearly as the temperature gradually
ground-state Debye temperatures of HfFe, HfRu and HfOs increases. Besides, it can be found that the order of ΘD in
using the quasi-harmonic Debye model are 338, 331 and the same temperature and pressure is HfFe > HfRu > HfOs.
307 K, respectively, which are slightly smaller than those Generally, a higher Debye temperature corresponds to a
values using the method based on elastic modulus (357 K material with a smaller thermal expansion coefficient and
for HfFe, 348 K for HfRu and 332 K for HfOs) [31]. From a stronger atomic bond. This is confirmed by the thermal
Fig. 13, when the temperature is low, the Θ D values of expansion coefficients and electronic structures of these
HfTM (TM = Fe, Ru, Os) compounds increase slightly HfTM compounds.

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Fig. 14  Variations of Grüneisen parameter as a function of temperature and pressure of HfTM compounds. a HfFe, b HfRu and c HfOs

Furthermore, the Grüneisen parameter describes the Acknowledgements This work was supported by the YNU East-Land
effect that changing the volume of a crystal lattice has on Scholar Research Fund under Grant No. C176220200, and Applied
Basic Research Program of Yunnan Province under Grant Nos.
its vibrational properties, and, as a consequence, the effect 2018FD012 and XJ2019002502.
that changing temperature has on the size or dynamics of
the lattice. The Grüneisen parameter γ vs. temperature and
pressure of HfTM compounds are plotted in Fig. 14. As
shown in Fig. 14, the value of γ increases with the tem- References
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